CN107526257B

CN107526257B - Toner, toner containing unit, image forming apparatus and image forming method

Info

Publication number: CN107526257B
Application number: CN201710452268.2A
Authority: CN
Inventors: 守屋彻; 松下奈津子
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2016-06-15
Filing date: 2017-06-15
Publication date: 2020-11-24
Anticipated expiration: 2037-06-15
Also published as: CN107526257A

Abstract

The invention provides a toner which has excellent low-temperature fixing property, pulverizability, charging property, transfer product blocking resistance, stress resistance and film forming resistance, is low in cost and has high environmental safety. Which contains at least a binder resin, and 1480 to 1520cm of the toner measured by FT-IR method and ATR method^‑1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^‑1The peak ratio (W/R) of the maximum peak height R of the spectrum derived from the carbonyl group in (1) is 0.20 to 0.70, the absorption spectrum of the toner measured by a transmission method using a spectrophotometer has a peak A at a wavelength of 350 to 390nm, the molecular weight distribution obtained from THF-soluble components in the toner is 1000 to 10000 as measured by GPC, the main peak is present, the half width of the molecular weight distribution is not more than 20000, and the THF-insoluble component is contained in an amount of 5 to 40% by mass.

Description

Toner, toner containing unit, image forming apparatus and image forming method

Technical Field

The invention relates to a toner, a toner containing unit, an image forming apparatus, and an image forming method.

Background

Generally, a toner used in a copying machine, a printer, or the like of an electrophotographic system is a mixture mainly composed of a binder resin and a plurality of substances such as a colorant, a releasing agent, and a charge control agent. In the pulverized toner, the raw materials are usually melt-kneaded, and the melt-kneaded product is pulverized and classified to obtain a toner having a desired particle diameter. The ratio of the binder resin among the raw materials constituting the toner is usually 80 to 90% by mass, and most of the components in the toner become the binder resin.

Recently, from the viewpoint of reducing power consumption and environmental load in a copying machine, a binder resin is generally a polyester resin which is easily fixable even with a low fixing temperature toner. In general, polyester resins for toners have a bisphenol a skeleton in an alcohol monomer constituting the resin, and therefore, have excellent low-temperature fixability and sharp melting properties, and therefore, have excellent gloss, and are particularly suitable for color toners. However, there is a problem that the pulverizability is poor at the time of toner production. In addition, although polyester resins for toners have excellent low-temperature fixability, when a large amount of printing paper is stacked upon one another during continuous paper discharge from a copying machine, such as in the field of high-speed machines, sticking between printed sheets, so-called "transfer blocking", is likely to occur, and improvement in blocking resistance is a major problem.

In order to achieve both excellent low-temperature fixability and pulverizability, resins having a reduced bisphenol a skeleton in the polyester resin have been proposed. Patent document 1 proposes a resin for toner and a toner composition, each of which is composed of a polyester resin obtained by polycondensation of an ethanol component and a carboxylic acid component.

The polyester resin has a carboxylic acid component comprising 80 to 100 mol% of terephthalic acid, isophthalic acid, and/or a lower alkyl (carbon number of alkyl group: 1 to 4) ester thereof, an ethanol component comprising 20 to 100 mol% of an aliphatic diol (85 to 100 mol% of the aliphatic diol is 1, 2-propanediol), and 0.1 to 20 mol% of a polyhydric alcohol having a valence of 3 or more and/or a carboxylic acid having a valence of 3 or more in the total of the ethanol component and the carboxylic acid component.

Conventionally, an aliphatic alcohol has been used as the ethanol component in order to provide a bisphenol a skeleton in the ethanol component. However, in this method, even if the low-temperature fixing property and the pulverizability can be improved, since the bisphenol a skeleton is reduced, there is a fear that deterioration or the like is caused by stress at the time of stirring the toner in a developing device or the like, the stress resistance (durability) is deteriorated, or the filming resistance of a member such as an electrostatic latent image carrier (hereinafter also referred to as a photoreceptor) is deteriorated. Further, since the bisphenol a skeleton is reduced, the chargeability of the resin is reduced, or the moisture absorption is increased, there is a concern that the toner is reduced in charge, the background stain is deteriorated, and the toner is scattered. That is, this method is insufficient in achieving excellent fixing property, pulverizability, chargeability, stress resistance, blocking resistance, and blocking resistance.

[ patent document ]

[ patent document 1] Japanese patent No. 5138630

Disclosure of Invention

The present invention has been made in view of the above problems, and an object thereof is as follows:

provided is a toner having excellent durability.

Provided is a toner having excellent charging properties.

Provided is a low-cost toner having excellent low-temperature fixability, pulverizability during toner production, and anti-blocking property of a transfer product, and having excellent anti-filming property.

The present inventors have conducted studies to solve the above problems and found that 1480 to 1520cm of a toner measured by an FT-IR (Fourier transform Infrared Spectroscopy) method (total reflection method) using a FT-IR (Fourier transform Infrared Spectroscopy measurement device) contains at least a binder resin^-1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^-1Wherein the peak ratio (W/R) of the maximum peak height R of the spectrum derived from the carbonyl group is 0.20 to 0.70, the absorption spectrum of the toner measured by a transmission method using a spectrophotometer has a peak A at a wavelength of 350 to 390nm, and has a main peak at a molecular weight distribution of 1000 to 10000 determined by GPC as measured from a THF-soluble component in the toner, and the half width of the molecular weight distribution is 20000 or less and contains 5 to 40 mass% of a THF-insoluble component. The toner is excellent in low-temperature fixability, pulverizability during toner production, blocking resistance during copying, durability, and filming resistance, and the present invention has been completed.

That is, the toner of the present invention is a toner described below:

a toner containing at least a binder resin, the toner being characterized in that:

1480 to 1520cm of toner measured by FT-IR and ATR method^-1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^-1Wherein the peak ratio (W/R) of the maximum peak height R of the spectrum derived from the carbonyl group is 0.20 to 0.70, the absorption spectrum of the toner measured by a transmission method using a spectrophotometer has a peak A at a wavelength of 350 to 390nm, and has a main peak at a molecular weight distribution of 1000 to 10000 determined by GPC as measured from a THF-soluble component in the toner, and the half width of the molecular weight distribution is 20000 or less and contains 5 to 40 mass% of a THF-insoluble component.

The following describes the effects of the present invention:

the toner of the present invention, having the above-described configuration, has the effects of excellent durability, chargeability, low-temperature fixability, pulverizability during toner production, blocking resistance during copying, and filming resistance, and being low in cost.

Drawings

Fig. 1 is a sectional view showing a configuration of an image forming apparatus according to the present invention.

Fig. 2 is a sectional view showing a configuration of a process cartridge as one embodiment of a toner container according to the present invention.

Detailed Description

The toner, the developer accommodating unit, and the image forming apparatus according to the present invention will be described below with reference to the drawings. The present invention is not limited to the embodiments described below, and other embodiments, additions, modifications, deletions, and the like may be modified within the scope of the present invention as contemplated by those skilled in the art, and any embodiment may be included in the scope of the present invention as long as the operation and effect of the present invention are achieved.

In the present invention, "FT-IR" is used as a term meaning "fourier transform infrared spectroscopic measurement apparatus", and "ATR method" is used as a term meaning "total reflection method".

The toner of the present invention is a toner containing at least a binder resin, characterized in that:

1480 to 1520cm of toner measured by FT-IR and ATR method^-1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^-1Wherein the peak ratio (W/R) of the maximum peak height R of the spectrum derived from the carbonyl group is 0.20 to 0.70, the absorption spectrum of the toner measured by a transmission method using a spectrophotometer has a peak A at a wavelength of 350 to 390nm, and has a main peak at a molecular weight distribution of 1000 to 10000 determined by GPC as measured from a THF-soluble component in the toner, and the half width of the molecular weight distribution is 20000 or less and contains 5 to 40 mass% of a THF-insoluble component. In the present invention, "GPC" means "gel permeation chromatography".

The toner of the present invention will be described in detail below.

First, raw materials containing at least a binder resin are mixed in a formulation in a set ratio. Next, the mixture is melt-kneaded to obtain a melt-kneaded product, and the melt-kneaded product is pulverized and classified to obtain a toner.

The toner is 1480-1520 cm measured by FT-IR method and ATR method^-1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^-1The peak ratio (W/R) of the maximum peak height R of the spectrum derived from the carbonyl group in (1) is 0.20 to 0.70. 1480 to 1520cm of toner^-1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^-1The peak ratio (W/R) of the maximum peak height R in the spectrum derived from the carbonyl group in (1) is preferably 0.20 to 0.65, more preferably 0.20 to 0.60, and particularly preferably 0.20 to 0.55.

If the value of W/R is less than 0.20, the filming resistance and durability are deteriorated, and if the value of W/R exceeds 0.70, the pulverization resistance and blocking resistance in the production of the toner are deteriorated.

Further, the absorption spectrum of the toner measured by the transmission method using a spectrophotometer must have a peak A at a wavelength of 350 to 390 nm. The absorption spectrum has no peak value A in the wavelength range of 350-390 nm, and the charging performance is easy to reduce.

The value of W/R is 0.20 to 0.70, and the absorption spectrum has a peak value A at a wavelength of 350 to 390nm, so that the pulverization property in the production of the toner is excellent, and the charging property, the transfer blocking resistance, the durability and the anti-filming property are also excellent.

1480-1520 cm of the toner measured by infrared spectroscopy (KBr tablet method) using FT-IR^-1The peak height W' of the medium spectrum and 1700-1750 cm^-1The peak ratio (W '/R ') of the peak height R ' of the spectrum (D) is preferably in the range of 0.06 to 0.70, more preferably 0.06 to 0.60, and particularly preferably 0.06 to 0.45. The values of W '/R' are 0.06 or more, and therefore, the resistance to filming and the durability are good, while the values of W '/R' are 0.70 or less, and therefore, the grindability and the blocking resistance are excellent.

1480 to 1520cm of toner measured by FT-IR and ATR method^-1Maximum peak of spectrum (c)Height W of 1700-1750 cm^-1The peak ratio (W/R) of the maximum peak height R of the spectrum in (1) is 1480 to 1520cm of the toner measured by an infrared spectroscopy (KBr tablet method) using FT-IR^-1The peak height W' of the medium spectrum and 1700-1750 cm^-1The peak ratio (W '/R ') of the peak height R ' of the spectrum in (a) is preferably such that the following relationship is established between the peak ratio (W/R) and the peak ratio (W '/R '): (W '/R'). ltoreq (W/R).

By satisfying the relationship (W '/R') or less (W/R), the sheet is particularly excellent in stress resistance, blocking resistance and low-temperature fixability, and is also excellent in grindability and blocking resistance, and the above-mentioned various properties can be satisfied at a high level.

The ratio (W/R)/(W '/R') between the peak ratio (W/R) and the peak ratio (W '/R') is preferably 1.0 to 2.0.

The FT-IR spectrum value was measured by ATR method (total reflection method) or infrared spectroscopy (KBr tablet method) using "Thermo Nicolet NEXUS470 (manufactured by Thermo SCIENTIFIC)".

The absorption spectrum of the spectrophotometer was measured by using a "U-1900 type proportional beam spectrophotometer (manufactured by hitachi corporation)", and the intensity of transmitted light was measured to obtain the value of absorbance.

The toner of the present invention preferably contains a polyester resin as a binder resin, and the ethanol component constituting the polyester resin contains a bisphenol component.

Further, the polyester resin preferably contains a high molecular weight polyester resin (H form) and a low molecular weight polyester resin (L form), and the content of the bisphenol A component contained in the ethanol component of the L form is in the range of 20 to 100 mol%, more preferably 20 to 80 mol%, particularly preferably 20 to 50 mol%, based on the ethanol component of the L form. The content of the bisphenol A component contained in the ethanol component of the H form is in the range of 0 to 80 mol%, preferably 0 to 50 mol%, particularly preferably 0 to 40 mol%, based on the ethanol component of the H form. Further, it is preferable that the content (mol%) of the bisphenol a component contained in the ethanol component of the L-form is larger than the content (mol%) of the bisphenol a component contained in the ethanol component of the H-form.

By satisfying the above relationship, the sheet is particularly excellent in durability, charging property, blocking resistance and low-temperature fixing property, and is also excellent in pulverizability and blocking resistance, and the above-described various properties can be satisfied at a high level.

The content of bisphenol A in H and L can be determined by dissolving in deuterated chloroform¹The peak area ratio was calculated from the peaks of various ethanol monomers and acid monomers by H-NMR (JNM-ECX, manufactured by Nippon electronics Co., Ltd.).

The toner of the present invention contains at least a binder resin as a component. The polyester resin is most suitable for the binder resin from the viewpoint of low-temperature fixability, durability and the like, but resins other than the polyester resin may be used alone or in combination as long as the above properties are not impaired.

The polyester resin used in the present invention is obtained by polycondensation of ethanol and carboxylic acid. Examples of the above-mentioned ethanol include glycols such as ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol, etherified bisphenols such as 1, 4-bis (hydroxymethyl) cyclohexane and bisphenol a, other 2-valent ethanol monomers, and polyhydric alcohol monomers having a valence of 3 or more. Among them, preferred are aromatic diols such as etherified bisphenols such as bisphenol a and aliphatic diols having 2 to 6 carbon atoms in the ethanol component. Further, it is preferable that ethylene glycol or 1, 2-propylene glycol is contained as at least a part in the aliphatic diol.

The content of the aliphatic diol having 2 to 6 carbon atoms in the ethanol component is preferably in the range of 5 to 90 mol%, more preferably 10 to 90 mol%, and particularly preferably 15 to 85 mol%. If the content of the aliphatic diol having 2 to 6 carbon atoms in the ethanol component is less than 5 mol%, the durability and the filming resistance are deteriorated, and if it exceeds 90 mol%, the pulverization property and the transfer blocking resistance at the time of toner production are deteriorated. The ethanol component may be composed of an aromatic diol component in addition to the aliphatic diol component having 2 to 6 carbon atoms.

Examples of the carboxylic acid component include a 2-valent organic acid monomer, a 3-valent or higher polycarboxylic acid monomer, and the like.

Examples of the organic acid monomer having a valence of 2 include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid.

Examples of the polyvalent carboxylic acid monomer having a valence of 3 or more include 1, 2, 4-benzenetricarboxylic acid, 1, 2, 5-benzenetricarboxylic acid, 1, 2, 4-hexyltricarboxylic acid, 1, 2, 4-naphthalenetricarboxylic acid, 1, 2, 5-hexyltricarboxylic acid, 1, 3-dicarboxy-2-methylenecarboxypropane, 1, 2, 7, 8-octyltetracarboxylic acid and the like.

In the toner of the present invention, the above polyester resins may be used alone or in combination of plural kinds.

In general, polyester resins for toners have desired properties such as fixing properties by combining a high molecular weight polyester resin (hereinafter, also referred to as "H-form") and a low molecular weight polyester resin (hereinafter, also referred to as "L-form") in a plurality of ways. The THF-insoluble fraction is derived from H-isomer, and the THF-soluble fraction is derived from L-isomer and a part of H-isomer.

In view of thermal blocking resistance and durability, the resin composition preferably contains an H-isomer, and in the present invention, the ethanol component preferably contains a carbon atom number

The aliphatic diol of (1). The content of the aliphatic diol in the ethanol component of the H-form is preferably in the range of 20 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 60 to 100 mol%. In addition, it is preferable that the toner contains an L-form from the viewpoint of low-temperature fixability and pulverizability in toner production, and the ethanol component of the L-form may contain an aromatic diol component and a carbon atom number

The aliphatic diol of (1). The content of the aliphatic diol in the ethanol component is preferably 0 to 80 mol%, more preferably 20 to 80 mol%, and particularly preferably 50 to 80 mol%.

When the H-form and the L-form are combined, the H-form preferably contains a large amount of an aliphatic diol component, whereby the low-temperature fixing property, the pulverizability during toner production, and the blocking resistance of the transfer can be improved while maintaining the durability and the anti-filming property. The reason for this is that the low molecular weight polyester resin component (L-form) is likely to be cracked during pulverization in the production of the toner, and thus becomes an interface and is likely to be exposed on the surface of the toner, and the low molecular weight polyester resin component (L-form) contains a small amount of aliphatic diol component, that is, contains a large amount of aromatic diol component, and thus can maintain durability, filming resistance, and low-temperature fixing properties.

On the other hand, since the polyester resin component (H-form) of the high molecular weight material contains a large amount of the aliphatic diol component, the pulverization property and the blocking resistance at the time of toner production are good, and as a result, the above-described various properties can be satisfied at a high level.

The "high molecular weight material" and "low molecular weight material" of the polyester resin are determined by the following criteria:

the softening temperature of the high molecular weight material is 140 ℃ to 170 ℃ inclusive, and the softening temperature of the low molecular weight material is 90 ℃ to less than 140 ℃.

(softening temperature measuring method)

Using an overhead flow rate measuring device CFT-500 (manufactured by Shimadzu corporation), a mold having a diameter of 1mm was pressed with a pressure of 20kg/cm²Heating to 1cm at a temperature rise rate of 6 deg.C/min²The sample of (3) is measured at the time of melt-flowing out based on the temperature corresponding to 1/2 from the start point to the end point of the flowing out.

The W/R value of the present invention is a value mainly related to the content of bisphenol A contained in the L-form, and a toner showing a desired W/R value can be obtained by appropriately adjusting the amount of bisphenol A contained in the L-form.

The glass transition temperature (Tg) of the polyester resin is usually set in view of heat storage stability

In a range of (1), preferably

More preferably

Is particularly preferred

The toner has a molecular weight distribution of 1000 to 10000 as measured by GPC as determined from THF-soluble components of the toner, and has a main peak. More preferably 2000 to 8000, particularly preferably 3000 to 8000, and the half width of the distribution is preferably 20000 or less. When the above value is within the above range, a toner having excellent low-temperature fixability can be obtained. GPC (gel permeation chromatography) was measured by the following method.

First, the THF-soluble component and THF-insoluble component of the toner were determined as follows.

About 1.0g of the toner was weighed, and THF50g was added thereto and sufficiently dissolved to obtain a solution, and the solution was separated by a centrifuge and filtered at normal temperature using a quantitative filter paper of five types C according to JIS (P3801). The THF-soluble fraction was defined as the fraction contained in the solution passing through the filter paper, and the THF-insoluble fraction was defined as the filter paper residue.

Molecular weight distribution of GPC obtained from THF-soluble components of the toner the solution passing through the filter paper was used as a sample solution, and the molecular weight distribution was measured by the following method.

The column was stabilized in a hot chamber at 40 ℃ and at this temperature, Tetrahydrofuran (THF) was flowed as a solvent at a flow rate of lml/min, and 50 to 200. mu.l of a tetrahydrofuran sample solution of a resin with a sample concentration adjusted to 0.05 to 0.6 mass% was injected and measured. When the molecular weight of a sample (toner) is measured, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a polystyrene sample having a molecular weight of 6X 10 manufactured by Pressure Chemical company or Toyo soda industries, Inc²、2.1×10³、4×10³、1.75×10⁴、5.1×10⁴、1.1×10⁵、3.9×10⁵、8.6×10⁵、2×10⁶And 4.48X 10⁶The standard polystyrene sample of (4) is preferably at least about 10 standard polystyrene samples. And, detectingThe instrument uses an RI (refractive index) detector.

Further, the THF-insoluble matter of the toner is preferably contained in an amount of 5 to 40% by mass, more preferably 10 to 35% by mass, and by setting the THF-insoluble matter of the toner to the above range, a toner excellent in heat blocking resistance and stress resistance can be obtained.

The THF-insoluble content of the toner described above was the ratio (mass%) of the filter paper residue to the toner used.

The THF-insoluble matter of the toner is mainly derived from a high molecular weight material contained in the binder resin, and therefore, it is preferable to adjust the content of the high molecular weight material in the binder resin.

The half width of the molecular weight distribution measured by GPC, which is determined from the THF-soluble content of the toner, was determined as follows.

The horizontal axis represents molecular weight, the vertical axis represents concentration (mass ratio) at an arbitrary height, and the width (molecular weight) of the horizontal axis of a main peak at 50% of the peak top height of the main peak is defined as half width. When a different peak is found at the edge of the main peak or the like, the molecular weight of the peak including the edge is calculated. When a peak other than the main peak is present on the abscissa of 50% of the peak top height of the main peak, the difference between the highest molecular weight and the lowest molecular weight among the molecular weights indicated by the intersection of the abscissa and each peak is defined as half width.

Usable resins other than the polyester resin include the following:

polystyrene, chlorostyrene, poly-alpha-methylstyrene, styrene/chlorostyrene copolymers, styrene/propylene copolymers, styrene/butadiene copolymers, styrene/vinyl chloride copolymers, styrene/vinyl acetate copolymers, styrene/maleic acid copolymers, styrene/acrylate copolymers (styrene/methyl acrylate copolymers, styrene/ethyl acrylate copolymers, styrene/butyl acrylate copolymers, styrene/octyl acrylate copolymers, styrene/phenyl acrylate copolymers, etc.), styrene/methacrylate copolymers (styrene/methyl methacrylate copolymers, styrene/ethyl methacrylate copolymers, styrene/butyl methacrylate copolymers, styrene/phenyl methacrylate copolymer, etc.), styrene resins (including styrene or styrene-substituted monomer or copolymer), vinyl chloride resins, styrene/vinyl acetate copolymers, rosin-modified maleic acid resins, phenol resins, epoxy resins, polyethylene resins, polypropylene resins, ionomer resins, polyurethane resins, silicone resins, ketone resins, styrene/ethyl acrylate copolymers, xylene resins, polyvinyl butyral resins, etc., petroleum resins, hydrogen-added petroleum resins, etc., such as styrene/methyl methacrylate copolymers, styrene/acrylonitrile/acrylate copolymers, etc.

The above resins may be used alone or in combination of two or more. The method for producing the resin is not particularly limited, and any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be used.

The glass transition temperature Tg of the resin is preferably 50 ℃ or higher, more preferably 55 ℃ or higher, from the viewpoint of heat preservability, as in the case of the polyester resin.

The toner of the present invention preferably contains a charge control agent. As the charge control agent, conventionally known charge control agents such as nigrosine dyes, metal complex salt dyes, quaternary ammonium salts and the like can be used alone or in combination, but from the viewpoint of toner chargeability, azo metal-containing compounds are preferably used. In the toner of the present invention, the ethanol component in the binder resin preferably contains a carbon number

The aliphatic diol (b) is not particularly limited, and may be used in combination with any other component. Therefore, in the case of a negatively charged toner, an azo metal-containing compound having high charge imparting ability can be suitably used.

The metal complex in the azo-containing metal compound is preferably a metal having 3 or more levels in which the metal complex can be 6-coordinated, and examples of the metal having 3 or more levels include Al, Fe, Cr, Zr, and the like, and Fe which is not toxic is particularly preferable.

As the iron azo compound in the present invention, compounds represented by the following structural formulae (1) and (2) can be cited:

in the formula (1), A⁺Represents an ammonium ion.

In the structural formula (2), J⁺Represents an H ion, an alkali metal ion, an ammonium ion, or an alkylammonium ion.

The commercially available product of the compound represented by the above formula (1) is not particularly limited, and examples thereof include T-77 manufactured by Gekko Swinhonis chemical Co.

The commercially available product of the compound represented by the above structural formula (2) is not particularly limited, and examples thereof include T-159 available from Gekko Swinhonis chemical Co.

The above-mentioned compounds may be used in combination of two or more.

The content of the azo metal-containing compound is preferably 0.5 to 3.0 parts by mass, more preferably 1.0 to 3.0 parts by mass, and particularly preferably 1.0 to 2.0 parts by mass, per 100 parts by mass of the binder resin in the toner, from the viewpoint of chargeability of the toner. When the content of the azo metal-containing compound is less than 0.5 parts by mass, the chargeability of the toner is insufficient, and when it exceeds 3.0 parts by mass, the toner charge amount is saturated, so that even if the content is increased, the cost is disadvantageous.

The volume average particle diameter Dv of the toner may be 4 to 6 μm. The volume average particle diameter of the toner is set to 4-6 μm, so that the toner adhesion amount per unit area (g/cm) on paper can be realized²) Therefore, it is advantageous in low-temperature fixability and fixing strength. However, when the volume average particle size is less than 4 μm, the content of the fine powder increases, and therefore, the member such as a photoreceptor is contaminated, the cleaning property is deteriorated, and an abnormal image is likely to occur.

In the present invention, as the releasing agent used for the toner, all known releasing agents can be used, and in particular, the free fatty acid type carnauba wax, montan wax, and oxidized rice wax can be used alone or in combination. The carnauba wax is preferably microcrystalline, has an acid value of 5 or less, and preferably has a particle diameter of 1 μm or less when dispersed in a binder resin. The montan wax is generally mineral refined montan wax, and is preferably microcrystalline, as in carnauba wax, and has an acid value of 5 to 14. The oxidized rice wax is obtained by air oxidation of rice bran wax, and the acid value of the oxidized rice wax is preferably 10-30. As other release agents, solid silicone varnish, higher fatty acid higher alcohol, lignite ester wax, low molecular weight polypropylene wax, and the like can be used, and any conventionally known release agent can be mixed. The amount of the release agent used is 1 to 20 parts by mass, preferably 3 to 10 parts by mass, based on the toner resin component.

In the present invention, a colorant may be used as a toner component, as needed. As the colorant, for example, carbon black, lampblack, iron black, aniline blue, phthalocyanine green, hansa yellow G, rhodamine lake, calco oil blue, chrome yellow, quinacridone pigment, benzidine yellow, rose bengal, triallylmethane dyes, and the like can be used, and any conventionally known colorant can be used alone or in combination, and can be used as a black toner or a color toner. The amount of the colorant used is usually 1 to 30 parts by mass, preferably 3 to 20 parts by mass, based on the toner resin component.

The toner of the present invention can be used as a magnetic toner containing a magnetic substance, and examples of the magnetic material contained in the toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, and alloys of metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof. In particular, magnetite is preferable in terms of magnetic properties.

The magnetic material preferably has an average particle diameter of about 0.1 to 2 μm, and the content thereof in the toner is about 15 to 200 parts by mass per 100 parts by mass of the resin component, and particularly preferably 20 to 100 parts by mass per 100 parts by mass of the resin component.

The toner of the present invention can be used as a one-component developer, and can also be used as a two-component developer combined with a carrier. When the toner of the present invention is used as a two-component developer, any known carrier can be used as the carrier, and examples thereof include magnetic powders such as iron powder, ferrite powder, and nickel powder, glass beads, and the like, and those having surfaces treated with a resin or the like. As the resin powder coated on the carrier of the present invention, there are styrene/propylene copolymer, silicone resin, maleic acid resin, fluorine-based resin, polyester resin, epoxy resin, and the like. In the case of a styrene/propylene copolymer, the styrene content is preferably 30 to 90 mass%. In this case, when the styrene content is less than 30% by mass, the developing property is low, and when it exceeds 90% by mass, the coating film becomes hard and easily peels off, and the carrier life becomes short. The resin coating layer of the carrier in the present invention may contain, in addition to the above-mentioned resin, an adhesion imparting agent, a curing agent, a lubricant, a conductive material, a charge control agent, and the like.

The toner of the present invention is filled in a container regardless of the use as a one-component developer or a two-component developer, and the container filled with the toner is generally different from the image forming apparatus and is distributed separately, and a user is attached to the image forming apparatus to form an image. As the container, for example, a conventional bottle type or cartridge type can be used, but the container is not limited thereto. The image forming apparatus is not particularly limited as long as it is an apparatus for forming an image by an electrophotographic method, and includes, for example, a copying machine and a printer.

(image Forming apparatus and image Forming method)

The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming means, a developing means, a transferring means, and a fixing means, and further includes other means as necessary.

The image forming method according to the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further includes other steps as necessary.

Electrostatic latent image carrier

The material, structure, and size of the electrostatic latent image carrier are not particularly limited, and may be appropriately selected from known products, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysiloxane and phthalide polymethine. Among them, amorphous silicon is preferable from the viewpoint of long life.

Electrostatic latent image forming means and electrostatic latent image forming process

The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and may be appropriately selected according to the purpose, and examples thereof include a means including at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for exposing the surface of the electrostatic latent image carrier to light to form an image. The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and may be appropriately selected according to the purpose, and for example, the electrostatic latent image carrier may be charged and then exposed to form an image, and the electrostatic latent image forming step may be performed using the electrostatic latent image forming means.

Charging member and charging

The charging member is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a contact charger known per se, which is provided with a conductive or semiconductive roller, brush, film, rubber sheet, and the like, and a non-contact charger using corona discharge such as a wire corona, a grid corona, and the like.

The charging may be performed by applying a voltage to the surface of the electrostatic latent image carrier using the charging member, for example. The shape of the charging member may be any shape such as a magnetic brush or a brush, in addition to the roller shape, and may be selected according to the specification or the shape of the image forming apparatus. The charging member is not limited to the contact type charging member, but a contact type charging member is preferable because an image forming apparatus that reduces ozone generated from the charging member can be obtained.

Exposure unit and exposure

The exposure means is not particularly limited as long as it can expose the surface of the electrostatic latent image bearing member charged by the charging means to obtain an image to be formed, and may be appropriately selected according to the purpose, and examples thereof include various exposure means such as a transfer optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. The light source used for the exposure member is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, Light Emitting Diodes (LEDs), semiconductor Lasers (LDs), and luminescent materials such as Electroluminescence (EL).

In order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter may be used. The exposure may be performed, for example, by exposing the surface of the latent electrostatic image bearing member to light using the exposure means to obtain an image.

In the present invention, a light back system in which an image is obtained by exposing the electrostatic latent image bearing member from the back side thereof may be employed.

Developing means and developing process

The developing means is not particularly limited as long as it is a developing means provided with a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image as a visible image, and can be appropriately selected according to the purpose.

The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible toner image, and may be appropriately selected according to the purpose, and may be performed by the developing means, for example. As the developing means, the following developing devices are preferable: the developing device includes a stirrer for charging the toner by friction stirring, and a magnetic field generating means fixed inside the stirrer, and includes a rotatable developer carrier for placing a developer containing the toner on a surface of the developer carrier.

Developer for developing images

The developer of the present invention contains at least the above toner, and if necessary, other components such as a carrier, which are appropriately selected.

When used in a high-speed printer or the like which is compatible with recent improvement in information processing speed, a two-component developer composed of a toner and a carrier is preferable because of an improvement in lifetime.

Vectors

The carrier is not particularly limited and may be appropriately selected according to the purpose, and is preferably a carrier including a core material and a resin layer covering the core material.

The material of the core material is not particularly limited and may be appropriately selected according to the purpose, and examples thereof include a manganese-strontium-based material of 50emu/g to 90emu/g, a manganese-magnesium-based material of 50emu/g to 90emu/g, and the like. In order to secure image density, a highly magnetic material such as iron powder of 100emu/g or more, magnetite of 75 to 120emu/g, or the like is preferably used. Further, since the impact of the developer in the fringe standing state on the photoreceptor can be alleviated, and the high image quality is facilitated, it is preferable to use a low-magnetization material such as copper-zinc based material of 30 to 80 emu/g.

The volume average particle diameter of the core material is not particularly limited and may be appropriately selected according to the purpose, but is preferably 10 to 150 μm, and more preferably 40 to 100 μm. When the volume average particle diameter is 10 μm or more, the amount of fine particles in the carrier is small, the magnetization of each fine particle is reduced, and carrier scattering does not occur, and when the volume average particle diameter is 150 μm or less, the specific surface area is not reduced, toner scattering does not occur, and the reproduction of the central portion of a color portion having a large solid portion is not deteriorated.

When the toner is used in a two-component developer, the toner may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected according to the purpose, but is preferably 90 to 98 parts by mass, and more preferably 93 to 97 parts by mass, based on 100 parts by mass of the two-component developer.

The developer of the present invention can be suitably used for forming an image by various known electrophotographic methods such as a magnetic single-component developing method, a non-magnetic single-component developing method, a two-component developing method, and the like. In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of a rotating magnetic roller in an ear-standing state to form a magnetic brush. The magnetic roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnetic roller moves to the surface of the electrostatic latent image carrier by the electric attraction. As a result, the electrostatic latent image is developed by the toner, and a visible image is formed on the surface of the electrostatic latent image carrier by the toner.

Transfer means and transfer Process

The transfer means is not particularly limited as long as it is a means for transferring a visible image onto a recording medium, and may be suitably selected according to the purpose, and preferably has an embodiment having a primary transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium.

The transfer step is not particularly limited as long as it is a step of transferring the visible image to a recording medium, and may be appropriately selected according to the purpose, and it is preferable to use an intermediate transfer member to primarily transfer the visible image to the intermediate transfer member and then secondarily transfer the visible image to the recording medium. In the transfer step, the photoreceptor may be charged by using, for example, a transfer charger, and the visible image may be transferred by the transfer means.

In the case where the image secondarily transferred to the recording medium is a color image formed of multicolor toners, the image may be formed on the intermediate transfer member by sequentially superimposing the respective toners on the intermediate transfer member by the transfer means, and the image on the intermediate transfer member may be secondarily transferred to the recording medium at once by the intermediate transfer means.

The intermediate transfer member is not particularly limited, and may be suitably selected from known transfer members according to the purpose, and examples thereof include a transfer belt.

The transfer means (the first transfer means, the second transfer means) is preferably provided with at least a transfer device for separating and charging the visible image formed on the photoreceptor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

The recording medium is typically plain paper, but is not particularly limited as long as an unfixed image after development can be transferred, and may be appropriately selected according to the purpose, and a PET substrate for OHP or the like may be used.

Fixing means and fixing Process

The fixing means is not particularly limited as long as it is a means for fixing the transferred image transferred onto the recording medium, and may be appropriately selected according to the purpose, and a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt. The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and may be appropriately selected according to the purpose, and for example, the visible image may be transferred to the recording medium separately for each color toner, or may be simultaneously transferred in a state of being stacked for each color toner at once.

The fixing step may be performed by the fixing means.

The heating of the heating and pressing member is preferably 80 to 200 ℃.

In the present invention, a known optical fixing device may be used in addition to or instead of the fixing means according to the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected according to the purpose, and is preferably 10N/cm²～80N/cm²。

Other means and other processes

Examples of the other means include a cleaning means, a power eliminating means, a recycling means, and a control means. Examples of the other steps include a cleaning step, a power-eliminating step, a recycling step, and a control step.

Cleaning means and cleaning Process

The cleaning means is not particularly limited as long as it is a means capable of removing the toner remaining on the photoreceptor, and may be appropriately selected according to the purpose, and examples thereof include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a wet cleaner.

The cleaning step is not particularly limited as long as it is a step capable of removing the toner remaining on the photoreceptor, and may be appropriately selected according to the purpose, and may be carried out by the cleaning means, for example.

Electricity eliminating means and procedure

The charge eliminating means is not particularly limited as long as it is a means for applying a charge eliminating bias to the photoreceptor to eliminate charge, and may be appropriately selected according to the purpose, and examples thereof include a charge eliminating brush.

The charge eliminating step is not particularly limited as long as it is a step of applying a charge eliminating bias to the photoreceptor to eliminate charge, and may be appropriately selected according to the purpose, and may be carried out by the charge eliminating means, for example.

Means and Process for Recycling

The reusing means is not particularly limited as long as it is a means for reusing the toner removed by the cleaning means in the developing device, and may be appropriately selected according to the purpose, and examples thereof include a known carrying means and the like.

The recycling step is not particularly limited as long as it is a step of recycling the toner removed in the cleaning step to the developing device, and may be appropriately selected according to the purpose, and may be performed by the recycling means, for example.

An embodiment of a method for forming an image by an image forming apparatus according to the present invention will be described below with reference to fig. 1.

The image forming apparatus 1 is a printer, but is not particularly limited as long as it is an apparatus for forming an image with toner, such as a copying machine, a facsimile machine, and a multifunction peripheral. The image forming apparatus 1 includes a paper feeding portion 210, a conveying portion 220, an image forming portion 230, a transfer portion 240, and a fixing device 250.

The paper feed unit 210 includes a paper feed cassette 211 on which the paper P to be fed is placed, and a paper feed roller 212 that feeds the paper P placed on the paper feed cassette 211 one by one.

The conveying unit 220 includes a roller 221 for conveying the sheet P fed by the sheet feeding roller 212 in the direction of the transfer unit 240, a pair of synchronization rollers 222, and a sheet discharging roller 223 for discharging the sheet P to which the color toner image is fixed to a sheet discharging tray 224. The pair of synchronization rollers 222 sandwiches the leading end portion of the paper P conveyed by the roller 221 and waits, and feeds the paper P to the transfer unit 240 at a set timing. The image forming portion 230 is provided with an image forming unit Y for forming an image using a developer having yellow toner, an image forming unit C for forming an image using a developer having cyan toner, an image forming unit M for forming an image using a developer having magenta toner, an image forming unit K for forming an image using a developer having black toner, and an exposure device 233 in this order from the left to the right at set intervals as shown in the drawing.

When any image forming means is indicated, the image forming means (Y, C, M, K) is referred to as an image forming means.

Also, the developer includes a toner and a carrier.

The four image forming units (Y, C, M, K) are different in the mechanical constitution by using different developers.

The transfer section 240 includes a driving roller 241, a driven roller 242, an intermediate transfer belt 243, primary transfer rollers (244Y, 244C, 244M, 244K), a secondary counter roller 245, and a secondary transfer roller 246. The intermediate transfer belt 243 is rotatable counterclockwise as shown in the figure with the driving of the driving roller 241, and primary transfer rollers (244Y, 244C, 244M, and 244K) are provided to face the photosensitive drum 231, and a secondary facing roller 245 and a secondary transfer roller 246 are provided to face each other across the intermediate transfer belt 243 at a transfer position of a toner image to paper.

The heater of the fixing device 250 is provided inside, the fixing belt 251 heats the paper P, and the fixing device 250 is provided with a pressure roller 252 which forms a nip portion by rotatably pressing against the fixing belt 251. Thereby, heat and pressure are applied to the color toner image on the paper P, and the color toner image is fixed. The sheet P on which the color toner image is fixed is discharged to the sheet discharge tray 224 by the sheet discharge roller 223, and a series of image forming processes are completed.

The toner containing unit in the present invention is a unit that contains toner and has a function of containing toner. Examples of the form of the toner containing unit include a toner container, a developing device, and a process cartridge. The toner container is a container for containing toner.

The developing device is a device that contains toner and performs development. The process cartridge is a cartridge that integrates at least an image carrier and a developing means, contains toner, and is attachable to and detachable from an image forming apparatus. The process cartridge may further include at least one means selected from a charging means, an exposure means, and a cleaning means.

When the toner containing unit of the present invention is attached to an image forming apparatus to form an image, the toner containing unit of the present invention forms an image from a low-cost toner having excellent durability, low-temperature fixing property, pulverizability at the time of toner production, blocking resistance of a copy, and filming resistance of the present invention, and therefore, has an effect that a good image can be obtained at low cost.

(processing card case)

The invention relates to a processing card box which is formed to be detachable relative to each image forming device and is provided with an electrostatic latent image carrier for carrying an electrostatic latent image and a developing means. The developing means develops the electrostatic latent image placed on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The process cartridge of the present invention may further comprise other means as necessary.

The developing means includes at least a developer container for containing the developer of the present invention, and a developer carrier for carrying the developer contained in the developer container. The developing means may further include a regulating member for regulating a thickness of the developer to be carried.

FIG. 2 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes the photosensitive body drum 10, the corona charger 58, the developer 40, the transfer roller 80, and the cleaning device 90.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The resins used in the examples are shown in tables 1 and 2, and the evaluation methods of the properties are shown in table 3.

In the following description, "part" means "part by mass" unless otherwise specified.

The method for evaluating the characteristics of the toner produced in each example is explained below:

[ evaluation method ]

[ 1] Low temperature fixability

A copier (MF2200) made by koshiko used a teflon (registered trademark) roller as a fixing roller, and a 6200 type paper made by koshiko was placed on the copier by using a device modified from the fixing unit of the copier, and a copy test was performed. The fixing temperature is changed, and the temperature at which cold blocking starts (fixing lower limit temperature) is obtained. The lower limit fixing temperature of the conventional low temperature fixing toner is about 140 to 150 ℃.

The evaluation conditions for low-temperature fixing were set as follows:

paper feed linear velocity: 120 to 150mm/sec

Surface pressure: 1.2Kgf/cm²

Clamping width: 3mm

The characteristic evaluation criteria are as follows:

(evaluation criteria)

Excellent performance of 130 ℃ above and 140 ℃ below zero.

O140 ℃ or higher but less than 150 ℃.

And delta is above 150 ℃ and below 160 ℃.

X is over 160 ℃.

[ 2] film resistance

Using a copier (MP9001) made by yu-ko corporation, 100 sheets of printing were continuously performed, and the film formation occurred on the electrophotographic photoreceptor by repeating 50 times. The surface of the photoreceptor was visually observed, and the occurrence of the consolidation of the toner component to the photoreceptor was evaluated according to the following evaluation criteria.

Very good performance no occurrence

Slightly occurs

Delta-number point occurrence

X is a large amount of

[ 3] chargeability

30 ten thousand prints were continuously made using a copier (MP9001) made by Yuguang corporation. The charge amount before and after printing was measured, and the charge reduction and toner scattering state after printing were evaluated. The toner scattering state was evaluated visually. The charge reduction is obtained by collecting a small amount of developer before and after printing from the jacket, and obtaining the charge amount by the ejection method and the reduction amount after printing.

The evaluation criteria are as follows:

excellent charging property was less than 1. mu.C/g, and toner scattering did not occur.

The chargeability was reduced to 1. mu.C/g or more and less than 10. mu.C/g, but toner scattering did not occur.

The charging property was reduced to 10. mu.C/g or more and less than 20. mu.C/g, and toner scattering was also caused.

In this case, the chargeability was reduced to 20. mu.C/g or more, and toner scattering occurred.

[ 4] durability

30 ten thousand prints were continuously made using a copier (MP9001) made by Yuguang corporation. The solidified state of the toner on the developing sleeve after printing was observed.

Excellent performance is not generated.

O occurs slightly at the end.

Δ full face occurred but could be wiped off.

The whole surface of the sleeve was fixed and could not be wiped off even by wiping.

[ 5] replica adhesion resistance

The white paper and the test chart (one printed alternately with black and solid image portions and white and exposed image portions) were alternately stacked in five sheets, and then heated at 75 ℃ for 6 hours under pressure and then naturally cooled for 1 hour. Thereafter, the ID of the transfer portion to the blank sheet and the ID of the non-transfer portion are measured, and the difference (Δ ID) is obtained. The higher the Δ ID, the poorer the blocking resistance. The evaluation criteria are as follows:

excellent performance less than 0.001.

O is 0.001 or more but less than 0.008.

And the delta is more than 0.008 and less than 0.01.

More than 0.01 percent of x.

Pulverizability [ 6]

The volume average particle diameter when the coarsely pulverized material (mesh 1.5mm) was pulverized at 9800rpm by a mechanical pulverizer (blade mill T250) was evaluated. The evaluation criteria are as follows:

very good less than 6.5 μm.

O6.5 μm or more but less than 7.0. mu.m.

And a particle size of 7.0 μm or more but less than 7.5. mu.m.

X is 7.5 μm or more.

(7) cost

The amount of bisphenol a contained in the ethanol component of the entire toner was determined by adding the bisphenol a content (mol%) contained in the ethanol component of the L-form and the bisphenol a content (mol%) contained in the ethanol component of the H-form of the polyester resin contained in the toner, and evaluation was performed. If the amount of bisphenol A is large, the cost is high.

The evaluation criteria are as follows:

very good is less than 0 to 66 mol%.

At least 66 mol% and less than 140 mol%.

The molar ratio is 140 mol% or more and less than 171 mol%.

Wherein the molar ratio of the metal oxide to the metal oxide is 171 mol% or more and less than 200 mol%.

(production of polyester)

The raw materials (ethanol component and acid component) shown in tables 1 and 2 were charged into a 1-liter four-neck round-bottomed flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen gas inlet tube, the flask was placed in a mantle resistance heater, nitrogen gas was introduced from the nitrogen gas inlet tube so that the inside of the flask was kept in an inert atmosphere, and the temperature was raised in this state, and then 0.05g of dibutyltin oxide was added so that the temperature was kept at 200 ℃ to carry out a reaction, thereby obtaining polyester resins a to K.

[ example 1]

The mixture having the above composition was sufficiently stirred and mixed in a henschel mixer, then heated and melted at a temperature of 130 to 140 ℃ for about 30 minutes by a roll mill, cooled to room temperature, and then the obtained kneaded product was coarsely pulverized by a coarse pulverizer (mesh 1.5mm), and pulverized and classified by a jet pulverizer, a mechanical pulverizer, or an air classifier, thereby obtaining a toner base having a volume average particle diameter of 6.8 μm. To the resultant toner base, 0.5 mass% of hydrophobic silica was added and mixed to prepare a final toner.

[ example 2]

Toner was obtained in the same manner as in example 1 except that the polyester resin A in example 1 was changed to the polyester resin B, the polyester resin G was changed to the polyester resin H, and the metal (iron) -containing azo compound (T-77) was changed to 3 parts.

[ example 3]

A toner was obtained in the same manner as in example 1 except that the polyester resin a in example 1 was changed to the polyester resin C and the polyester resin G was changed to the polyester resin I.

[ example 4]

Toner was obtained in the same manner as in example 1 except that the charge control agent (T-77) in example 1 was changed to the metal (iron) -containing azo compound (T-159).

[ example 5]

A toner was obtained in the same manner as in example 1 except that the charge controlling agent (T-77) in example 1 was changed to 3 parts.

[ example 6]

A toner was obtained in the same manner as in example 1 except that the polyester resin a in example 1 was changed to the polyester resin D and the polyester resin G was changed to the polyester resin H.

[ example 7]

A toner was obtained in the same manner as in example 1 except that the polyester resin a in example 1 was changed to the polyester resin E and the polyester resin G was changed to the polyester resin J.

[ example 8]

A toner was obtained in the same manner as in example 1 except that the volume average particle diameter of the toner base obtained in example 1 was changed to 5.2 μm.

Comparative example 1

Comparative example 2

A toner was obtained in the same manner as in comparative example 1 except that the polyester resin B in comparative example 1 was changed to the polyester resin F and the polyester resin K was changed to the polyester resin J.

Comparative example 3

A toner was obtained in the same manner as in comparative example 1 except that the polyester resin B in comparative example 1 was changed to the polyester resin D, the polyester resin K was changed to the polyester resin H, and the metal (iron) -containing azo compound (T-77) was changed to Zn salicylate (E-304, manufactured by ORIENT Chemicals).

Comparative example 4

Toner was obtained in the same manner as in comparative example 1 except that the polyester resin B in comparative example 1 was changed to polyester resin D, the polyester resin K was changed to polyester resin H, and the metal (iron) -containing azo compound (T-77) was changed to an organoboron complex (LR-147: manufactured by CARLIT, Japan).

Comparative example 5

Toner was obtained in the same manner as in comparative example 1 except that the polyester resin B in comparative example 1 was changed to the polyester resin D, the polyester resin K was changed to the polyester resin H, and the metal (iron) -containing azo compound (T-77) was changed to the Zr salicylate compound (TN-105).

The combinations of the polyester resins in the examples and comparative examples are shown in table 3.

The method for measuring the physical property values (weight average molecular weight, maximum peak molecular weight, etc.) of the polyester resin may be a generally known method, and the description thereof will be omitted.

TABLE 1

TABLE 2

TABLE 3-1

TABLE 3-2

Tables 3 to 3

(example 1)

Example 1 as a result of combining a resin having a bisphenol a content of 50 mol% in the ethanol component of the L body which becomes a soluble component when dissolved in THF and a resin having a bisphenol a content of 90 mol% in the ethanol component of the H body which becomes an insoluble component when dissolved in THF, the configuration of the present invention was satisfied. The value of W '/R' is 0.70 or more, and bisphenol A is contained in the toner in a large amount, so that the pulverization property and cost are also a large value.

Since the contents of bisphenol a in both H and L bodies are large, the toner charging is hardly reduced, and the chargeability is good.

(example 2)

Example 2 as a result of combining a resin having a bisphenol a content of 30 mol% in the ethanol component of the L body which becomes a soluble component when dissolved in THF and a resin having a bisphenol a content of 0 mol% in the ethanol component of the H body which becomes an insoluble component when dissolved in THF, the configuration of the present invention was satisfied. All the properties are well balanced and satisfactory, and the aliphatic diol is contained in a large amount in the THF-insoluble matter, resulting in good pulverizability. Since the toner contains a small amount of bisphenol a, the toner is also excellent in the transfer blocking resistance.

Further, although the toner is likely to suffer from a decrease in toner charge due to a small bisphenol a content, the inclusion of 3 parts of T-77 results in good chargeability.

(example 3)

Example 3 as a result of combining a resin having a bisphenol a content of 60 mol% contained in the ethanol component of the L body which becomes a soluble component when dissolved in THF and a resin having a bisphenol a content of 55 mol% contained in the ethanol component of the H body which becomes an insoluble component when dissolved in THF, the configuration of the present invention was satisfied, and all the characteristics were evaluated to be good.

(example 4)

Example 4 the same resin composition as that of example 1 was used except that the kind of the charge control agent was different from that of example 1, except that the resin having a bisphenol a content of 50 mol% in the ethanol component of the L-form which becomes a soluble component when dissolved in THF and the resin having a bisphenol a content of 90 mol% in the ethanol component of the H-form which becomes an insoluble component when dissolved in THF were combined. Since both the H-isomer and the L-isomer had a large content of bisphenol A, the toner was less likely to be reduced in charging, and T-159, which is a charge control agent, had an improved charging property and was excellent compared with T-77 used in example 1.

(example 5)

Example 5 the same resin composition as that of example 1 was used except that the number of charge control agents was different from that of example 1 in the case of combining a resin having a bisphenol a content of 50 mol% in the ethanol component of the L form which becomes a soluble component when dissolved in THF and a resin having a bisphenol a content of 90 mol% in the ethanol component of the H form which becomes an insoluble component when dissolved in THF. Since both the H-isomer and the L-isomer contained a large amount of bisphenol A, the toner was less likely to be reduced in charging, and the inclusion of 3 parts of T-77 improved the charging property and became excellent compared with 1 part of example 1.

(example 6)

Example 6 as a resin, when dissolved in THF, the resin containing 30 mol% of bisphenol a contained in the L-form ethanol component, which becomes a soluble component, and the resin containing 20 mol% of bisphenol a contained in the H-form ethanol component, which becomes an insoluble component, were combined, the configuration of the present invention was satisfied. All properties are satisfied in a well-balanced manner, and the aliphatic diol is contained in a large amount in the THF-insoluble matter, so that the grindability is good, and the THF-insoluble matter is contained in 35% by mass, so that the durability is also good. Further, since the content of bisphenol A in both H and L forms is small, the toner charging tends to be lowered, but the charging property is good when 1 part of T-77 is contained.

(example 7)

Example 7 as a resin, when dissolved in THF, the resin containing 100 mol% of bisphenol a contained in the ethanol component of the L body which becomes a soluble component and the resin containing 35 mol% of bisphenol a contained in the ethanol component of the H body which becomes an insoluble component were combined, and as a result, the configuration of the present invention was satisfied. Since the THF-soluble component, which is an L-form that is easily exposed on the toner surface, contains a large amount of an aromatic diol component, the low-temperature fixing property, the filming resistance, and the durability are excellent.

Further, since the THF-insoluble matter was present in a small amount of 5% by mass, the grindability was also good.

Further, since a large amount of aromatic diol component is contained in the THF-soluble component as the L-form which is easily exposed to the toner surface, the toner charging is less likely to be reduced, and the charging property is also good as a result of containing 1 part of T-77.

(example 8)

Example 8 as a resin, when dissolved in THF, the resin containing 50 mol% of bisphenol a contained in the L-form ethanol component, which becomes a soluble component, and the resin containing 90 mol% of bisphenol a contained in the H-form ethanol component, which becomes an insoluble component, were combined, the configuration of the present invention was satisfied. The value of W '/R' is 0.70 or more, and bisphenol A is contained in the toner in a large amount, so that the pulverization property and cost are also a large value.

Since the contents of bisphenol a in both H and L bodies are large, the toner charging is hardly reduced, and the chargeability is good. Further, since the volume average particle size was small, i.e., 5.2 μm, the low-temperature fixability was excellent, but the filming resistance was Δ.

Comparative example 1

Comparative example 1 as a resin, the combination of the resin in THF dissolved becomes soluble components of L body, and dissolved in THF dissolved into insoluble components of H body in ethanol does not contain bisphenol A resin, because the combination of the resin, to resist replica blocking, grinding good results. However, the film formation resistance and durability were poor. Since neither the H-form nor the L-form contains bisphenol A, the toner has poor chargeability even when T-77 toner is used.

Comparative example 2

Comparative example 2 as a resin, the combination of the resin dissolved in THF becomes soluble components of L body, and dissolved in THF becomes insoluble components of H body in ethanol content containing 100% bisphenol A resin, because the combination of the resin, low temperature fixation, resistance to film formation, durability good results. However, this results in poor replica blocking resistance and chipping resistance.

Since both the H-isomer and the L-isomer contain 100% of bisphenol A, the toner is less likely to have reduced chargeability, resulting in good chargeability.

Comparative example 3

Comparative example 3 as a resin, when dissolved in THF and becomes soluble L body ethanol content containing bisphenol A content of 30 mol% resin and dissolved in THF and becomes insoluble H body ethanol content containing bisphenol A content of 20 mol% resin, because the THF insoluble component contains a large amount of aliphatic diol, grinding is good, because contains THF insoluble component 35 mass%, therefore, becomes good durability results. However, since the content of bisphenol A in both H-isomer and L-isomer is small, the toner charging tends to be lowered, and although a charge control agent is used, the charge control agent E-304 other than T-77 is used, and when it is measured by a transmission method using a spectrophotometer, there is no peak in the wavelength range of 350 to 390nm, resulting in poor charging properties.

Comparative example 4

Comparative example 4 as a resin, when dissolved in THF and becomes a soluble component of the L body of the ethanol content of bisphenol a content of 30 mol% and dissolved in THF and becomes an insoluble component of the H body of the ethanol content of bisphenol a content of 20 mol% combined results, because the THF insoluble component contains a large amount of aliphatic diol, grinding is good, because contains THF insoluble component 35 mass%, therefore, becomes good durability results. However, since the content of bisphenol A in both H and L forms is small, the toner charging tends to be lowered, and although a charge control agent is used, the charge control agent LR-147 other than T-77 is used, and when it is measured by a transmission method using a spectrophotometer, there is no peak in the wavelength range of 350 to 390nm, resulting in poor charging properties.

Comparative example 5

Comparative example 5 as a resin, when dissolved in THF and becomes a soluble component of the L body of the ethanol content of bisphenol a content of 30 mol% and dissolved in THF and becomes an insoluble component of the H body of the ethanol content of bisphenol a content of 20 mol% combined results, because the THF insoluble component contains a large amount of aliphatic diol, grinding is good, because containing THF insoluble component 35 mass%, therefore, becomes good durability results. However, since the content of bisphenol A in both H-isomer and L-isomer is small, the toner charging tends to be lowered, and although a charge control agent is used, TN-105, which is a charge control agent other than T-77, is used, and when it is measured by a transmission method using a spectrophotometer, there is no peak in the wavelength range of 350 to 390nm, resulting in poor charging properties.

As described above, it is understood that the toners of the examples are excellent in low-temperature fixability, pulverizability at the time of toner production, and also excellent in copy blocking resistance, durability, and blocking resistance.

The above embodiments are merely examples suitable for implementing the present invention, and are not to be construed as limiting the technical scope of the present invention. That is, the present invention can be implemented in various other forms without departing from the spirit or gist of the present invention.

Claims

1. A toner containing at least a binder resin, wherein:

1480-1520 cm of toner measured by total reflection method using Fourier transform infrared spectroscopic analysis and measurement apparatus^-1The maximum peak height W of the spectrum from the bisphenol A skeleton in (1) and 1700-1750 cm^-1Wherein the peak ratio W/R of the maximum peak height R of the spectrum derived from the carbonyl group is 0.20 to 0.70;

an absorption spectrum of the toner measured by a transmission method using a spectrophotometer has a peak (A) at a wavelength of 350 to 390 nm;

and has a main peak value in a molecular weight distribution of 1000 to 10000 as determined by gel permeation chromatography based on tetrahydrofuran-soluble components in the toner, wherein the half width of the molecular weight distribution is 20000 or less;

and a THF-insoluble content of 5 to 40% by mass.

2. The toner according to claim 1, wherein:

1480-1520 cm of toner measured by KBr tablet method in infrared spectroscopy using Fourier transform infrared spectroscopy measurement apparatus^-1The peak height W' of the medium spectrum and 1700-1750 cm^-1The peak ratio W '/R ' of the peak height R ' of the spectrum in (1) is 0.06 to 0.70.

3. The toner according to claim 2, wherein:

the peak ratio W/R and the peak ratio W '/R' satisfy the following relationship: w '/R' is not more than W/R.

4. The toner according to any one of claims 1 to 3, wherein:

the binder resin is a polyester resin, and the diol component constituting the polyester resin contains a bisphenol A component.

5. The toner according to claim 4, wherein:

the polyester resin contains a high molecular weight H-body polyester resin and a low molecular weight L-body polyester resin, the content of a bisphenol A component contained in the diol component of the L-body in the toner is 20 to 100 mol% of the content of the diol component of the L-body, the content of a bisphenol A component contained in the diol component of the H-body in the toner is 0 to 80 mol% of the content of the diol component of the H-body, and the mol% of the bisphenol A component contained in the diol component of the L-body is more than the mol% of the bisphenol A component contained in the diol component of the H-body.

6. The toner according to claim 3, wherein:

the ratio W/R/W '/R' between the peak ratio W/R and the peak ratio W '/R' is 1.0 to 2.0.

7. The toner according to any one of claims 1 to 3, wherein:

the toner contains 10 to 35 mass% of a tetrahydrofuran insoluble component.

8. The toner according to any one of claims 1 to 3, wherein:

the toner contains a charge control agent.

9. The toner according to claim 8, wherein:

the charge control agent is an iron azo compound represented by the following structural formula (1):

in the formula (1), A⁺Represents an ammonium ion.

10. The toner according to claim 9, wherein:

the iron azo compound is 0.5 to 3.0 parts by mass based on 100 parts by mass of the binder resin.

11. The toner according to any one of claims 1 to 3, wherein:

the volume average particle diameter (Dv) of the toner is 4 to 6 μm.

12. A toner containing unit, wherein:

comprising the toner according to any one of claims 1 to 11.

13. An image forming apparatus, comprising:

an electrostatic latent image carrier;

a charging device for charging the electrostatic latent image carrier;

an electrostatic latent image forming device for forming an electrostatic latent image on the charged electrostatic latent image carrier;

a developing device containing toner for developing the electrostatic latent image formed on the electrostatic latent image carrier by using toner to form a toner image;

a transfer device for transferring the toner image formed on the electrostatic latent image carrier to a recording medium; and

a fixing device for fixing the toner image transferred on the recording medium;

the toner according to any one of claims 1 to 11.

14. An image forming method, comprising:

an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;

a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image;

a transfer step of transferring the toner image formed on the electrostatic latent image carrier to a recording medium; and

a fixing step of fixing the toner image transferred onto the recording medium;

the toner according to any one of claims 1 to 11.